PHY5052(Cold Atom Physics)

Chapter 1: Atomic structure

2023.03.03
 Recall on last class
Non-relativistic hydrogen atom:
ℏ2 𝛻𝑟2 𝑍𝑒 2
− − 𝜓 𝒓 = 𝐸𝜓 𝒓
2𝑚 4𝜋𝜖0 𝑟

𝜓 = 𝑅 𝑟 𝑌 𝜃, 𝜑
The angular part: the orbital angular momentum

2𝑙 + 1 𝑙 − 𝑚 ! 𝑚
𝑌𝑙𝑚 𝜃, 𝜙 = −1 𝑚
𝑃𝑙 cosθ 𝑒 ⅈ𝑚𝜙
4𝜋 𝑙+𝑚 !
𝐿𝑧 𝑌𝑙𝑚 𝜃, 𝜙 = 𝑚ℏ 𝑌𝑙𝑚 𝜃, 𝜙

𝐿2 𝑌𝑙𝑚 𝜃, 𝜙 = 𝑙(𝑙 + 1)ℏ 𝑌𝑙𝑚 𝜃, 𝜙

The radial part:
1 ⅆ ⅆ𝑅 2𝑚𝑟 2 −2𝑚 𝐸
𝑟2 − 2 𝑉 𝑟 − 𝐸 = 𝑙(𝑙 + 1) 𝜅≡
𝑅 ⅆ𝑟 ⅆ𝑟 ℏ ℏ
𝑚𝑒 2
𝜌 ≡ 𝜅𝑟 , and 𝜌0 ≡
2πϵ0 ℏ2 𝜅
𝑢(𝑟) ≡ 𝑟𝑅(𝑟) 𝑙+1 −𝜌
𝑢 𝜌 = 𝜌 𝑒 𝑣(𝜌)
2 𝑗 + 𝑙 + 1 − 𝜌0
𝑣 𝜌 = σ∞
𝑗=0 𝑎𝑗 𝜌
𝑗
𝑎𝑗+1 = 𝑎
(𝑗 + 1)(𝑗 + 2𝑙 + 2) 𝑗 2
 Recall on last class
Non-relativistic hydrogen atom:
The energy:
2
𝑚 𝑒2 1 𝑒2 1 𝑅𝑦
𝐸𝑛 = − 2 =− =− 2 𝑛 = 1, 2, 3, …
ℏ 4πϵ0 2 4πϵ0 𝑎0 𝑛2 𝑛
with: 𝑚𝑒 𝑒 4
4πϵ0 ℏ2
𝑎0 = 𝑅𝑦 = 2 2
𝑚𝑒 2 2ℏ 4𝜋𝜖0
The total wave function:
𝜓𝑛𝑙𝑚 𝑟, 𝜃, 𝜙 = 𝑅𝑛𝑙 𝑟 𝑌𝑙𝑚 (𝜃, 𝜙)
2 3 𝑛 − 𝑙 − 1 ! −𝑟/𝑛𝑎 2𝑟 𝑙 2𝑙+1 2𝑟 𝑚
𝜓𝑛𝑙𝑚 = ( ) 𝑒 ( ) 𝐿 𝑛−𝑙−1 𝑟 𝑌𝑙 (𝜃, 𝜙)
4𝑛𝑎 2𝑛[ 𝑛 + 𝑙 !]3 𝑛𝑎 𝑛𝑎

෠ 𝑛𝑙𝑚 𝑟, 𝜃, 𝜑 = −1 𝑙 𝜓𝑛𝑙𝑚 𝑟, 𝜃, 𝜑
𝑃𝜓

High degeneracy. For a given n,

1) l has n values: 𝑙 ≤ 𝑛 − 1
2) m has 2l+1 values with each l
3) total degeneracy: n2 3
 Recall on last class
Each u(r) has (n - l - 1) nodes (except for r=0) and for l ≠ 0, the wavefunction
vanishes at the origin.

Some important scaling rules:

1 1 2𝑅𝑦
ΔE =𝑅𝑦 2 − 2
≃ 3
𝑛 𝑛+1 𝑛
1
𝑟 = 𝑅𝑛𝑙 ❘𝑟❘𝑅𝑛𝑙 = 3𝑛2 − 𝑙 𝑙 + 1 𝑎0 ∝ 𝑛2
2
1 1 1 1 1 1 1
= 2 ∝ 2 = ∝
𝑟 𝑛 𝑎0 𝑛 𝑟2 𝑎0 2 𝑛3 𝑙 + 1Τ2 𝑛3
1 1 1 1
= 3 3 ∝
𝑟3 𝑎0 𝑛 (𝑙 + 1)(𝑙 + 1/2)𝑙 𝑛3

4
 Recall on last class
Rydberg atom: Ry
𝐸𝑛𝑙 = −
(𝑛 − 𝛿𝑛𝑙 )2

properties scaling
Energy 1/n2
Energy spacing 1/n3 𝑟 𝑠 ∝ 𝑛2𝑠
𝑟 −𝑠 ∝ 𝑛−3 for 𝑠 > 1
Radius and electric dipole moment n2
Radiative lifetime n3
Polarizability n7
Dipole-dipole interaction of 2 n4
Rydberg atoms
Van-del Waals interaction (𝐶6 ) n11

5
He atom

6
 Why Helium

It is just a 3-body problem, but exact solution is still impossible for now.

We will see that it is already much more complicated than H atom.

Direct comparison with experiments is possible.

7
 Why Helium
two electron atoms
➢ One electron → ൠ new thing: 𝑒 − − 𝑒 − replusion
multielectron atoms

➢ The inadequate of Bohr theory

➢ The spin multiplicity: singlet and triplet

8
 Helium: the Hamiltonian
ℏ2 2 ℏ2 2 𝑍𝑒 2 𝑍𝑒 2 𝑒2
𝐻 =− 𝛻 − 𝛻 − − +
2𝑚 1 2𝑚 2 4𝜋𝜖0 𝑟1 4𝜋𝜖0 𝑟2 4𝜋𝜖0 𝑟12

with Z=2,𝑟𝑖 = 𝒓𝑖 , 𝑟12 = 𝒓1 − 𝒓2

The S.E.
ℏ2 2 ℏ2 2 𝑍𝑒 2 𝑍𝑒 2 𝑒2
− 𝛻1 − 𝛻2 − − + 𝜓 = 𝐸𝜓
2𝑚 2𝑚 4𝜋𝜖0 𝑟1 4𝜋𝜖0 𝑟2 4𝜋𝜖0 𝑟12

𝜓 = 𝜓(𝒓1 , 𝒓2 )
Why He atom is harder to solve?
The Hamiltonian has no spherical symmetry anymore: can’t separate
radial and angular parts.

Exact solution impossible!

Approximation methods:
1. perturbation: need to higher order
2. Variational method 9
 Helium: the ground state
A very rough estimation Assume the two electrons are independent to each other

ℏ2 2 ℏ2 2 𝑍𝑒 2 𝑍𝑒 2
𝐻0 = − 𝛻 − 𝛻 − − = 𝐻1 + 𝐻2
2𝑚 1 2𝑚 2 4𝜋𝜖0 𝑟1 4𝜋𝜖0 𝑟2

Take the hydrogenic part of the wavefunction:

𝜓𝑔 𝒓1 , 𝒓2 = 𝜓 𝒓1 𝜓 𝒓2 = 𝑅10 (𝒓1 )𝑌00 (𝒓1 )𝑅10 (𝒓2 )𝑌00 (𝒓2 )
Substrate into S.E.:

𝐻0 𝜓𝑔 𝒓1 , 𝒓2 = 𝐸 (0) 𝜓𝑔 𝒓1 , 𝒓2 𝐻1 𝜓𝑔 + 𝐻1 𝜓𝑔 = (𝐸1 + 𝐸2 )𝜓𝑔

𝑍2
Remember: 𝐸𝑛 = − 2 𝑅𝑦
𝑛
For the ground state of two 1s electron: n=1, l=0, Z=2
𝐸 (0) = 𝐸1 + 𝐸2 = −4𝑅𝑦 − 4𝑅𝑦 = −108.8 𝑒𝑉
Binding energy of one electron is 54.4eV!
Real𝐸 (0) = −79.2 eV, about 35% difference:
𝒆− − 𝒆− interaction cannot be ignored. 10
 Helium: the ground state
First order perturbation: two independent electrons perturbed by their repulsive
interactions.
The 0th order wavefunction:

𝜓𝑔 𝒓1 , 𝒓2 = 𝜓 𝒓1 𝜓 𝒓2 = 𝑅10 (𝒓1 )𝑌00 (𝒓1 )𝑅10 (𝒓2 )𝑌00 (𝒓2 )

3/2
1 2
𝑌00 = , and 𝑅10 𝑟 = 2 𝑒 −2𝑟/𝑎0 , for Z=2
4𝜋 𝑎0

Following the perturbation theory, the first order correction is:

𝑒2
Δ𝐸 = 𝜓𝑔 4𝜋𝜖 𝑟 𝜓𝑔
0 12
3 2
2𝜋 𝜋 1 2 ∞ ∞ 2 𝑒2
= ‫׬‬0 ⅆ𝜙 ‫׬‬0 𝑠𝑖𝑛𝜃 ⅆ𝜃
4𝜋
‫׬‬0 𝑟22 ⅆ𝑟2 ‫׬‬0 𝑟12 ⅆ𝑟1 𝑎0
4 𝑒 −4(𝑟1+𝑟2)/𝑎0 ×
4𝜋𝜖0 𝑟1 −𝑟2
2
32 𝑒2 ∞ 2 ∞ 2 𝑒 −4(𝑟1 +𝑟2 )/𝑎0
= ‫ 𝑟 ׬‬ⅆ𝑟2 ‫׬‬0 𝑟1 ⅆ𝑟1 = 34 eV
𝑎0 3 4𝜋𝜖0 0 2 𝑟1 −𝑟2

𝑅𝑦 × 5/2
11
 Helium: the ground state
This is 30% of the main term, so repulsive electrostatic term is quite large!

𝐸 = 𝐸 (0) + Δ𝐸 = −109 + 34 = −75 eV

Only 4 eV away from the real value!

For further improvement, we can go to higher-order perturbation or use the

variational method.

12
 Helium:
Ionization theof ground
limits He atom state

Question:
1. What is the transition energy between ground state and the second
ionization limit, or from He (1s2) to He2+ ?
2. How about from the first ionization limit to the second, or He+ to He2+?
3. How about from He (1s2) to He+ ?

Answers:
1. ~79 eV
2. ~54 eV
3. ~25 eV

13
 Helium: the spin eigenstates
So far, we have ignored the Pauli exclusion...

The overall WF (spatial + spin) has to be anti−symmetric

for fermions (electrons) Notation:

𝑛 2𝑆+1 𝐿𝐽
Spin eigenstates
Independent
Total AM of
2
1 𝑠 : ground state the electron
1s2s: first excited state
1s2p: second excited state individual orbital AM
Individual spin AM
Coupled

𝑳 = σ𝑖 𝒍𝑖 , S= σ𝑖 𝒔𝑖 , 𝑱 = 𝑳 + 𝑺

Total orbital AM Total spin AM

14
 Helium: the spin eigenstates
Pauli exclusion principle: total WF (spatial + spin) be anti-symmetric for
electrons
𝜓𝑡𝑜𝑡𝑎𝑙 = 𝜓 𝑠𝑦𝑚𝑚𝑒𝑡𝑟𝑖𝑐 𝒓 𝜓 𝑎𝑛𝑡𝑖𝑠𝑦𝑚𝑚𝑒𝑡𝑟𝑖𝑐 𝜒
൝
𝜓𝑡𝑜𝑡𝑎𝑙 = 𝜓 𝑎𝑛𝑡𝑖𝑠𝑦𝑚𝑚𝑒𝑡𝑟𝑖𝑐 𝒓 𝜓 𝑠𝑦𝑚𝑚𝑒𝑡𝑟𝑖𝑐 𝜒

Electron spin
𝜓(𝜒)is the spin wavefunction. For two electrons with spin-1/2

1
𝜓 𝑎𝑛𝑡𝑖𝑠𝑦𝑚𝑚𝑒𝑡𝑟𝑖𝑐 𝜒 = (|↑↓ۧ − |↓↑ۧ): S=0 Spin singlet
2
1
𝜓 𝑠𝑦𝑚𝑚𝑒𝑡𝑟𝑖𝑐 𝜒 = |↑↑ۧ, |↓↓ۧ, 𝑜𝑟 (|↑↓ۧ + |↓↑ۧ): S=1 Spin triplet
2

So ground state: 1 1 𝑆0
First excite state: 2 1 𝑆0 or 2 3 𝑆1
Second excite state: 2 1 𝑃1 or 2 3 𝑃0,1,2
15
 Helium: the spin eigenstates
Independent
1 𝑠 2 : ground state
1s2s: first excited state
1s2p: second excited state

So ground state: 1 1 𝑆0
First excite state: 2 1 𝑆0 or 2 3 𝑆1
Second excite state: 2 1 𝑃1 or 2 3 𝑃0,1,2

Question: which has higher energy,

spin singlet or triplet? Why?

16
 Helium: the spin eigenstates

Possible transitions:

singlet-singlet,
triplet-triplet
No singlet-triplet

23S state is metastable:

lifetime 7870(510) seconds

PRL, 103,053002(2009)

So ground state: 1 1 𝑆0
First excite state: 2 1 𝑆0 or 2 3 𝑆1
Second excite state: 2 1 𝑃1 or 2 3 𝑃0,1,2 17
 Helium: the excited state
Wavefuction, hydrogen like (more general case |1snl>)
1
𝑢1𝑠 = 𝑅1𝑠 (𝑟1 ) ×
4𝜋
𝑢𝑛𝑙 = 𝑅𝑛𝑙 (𝑟2 )𝑌𝑙𝑚 (𝜃2 , 𝜑2 )

Spatial wavefuction, the product

𝜓𝑠𝑝𝑎𝑐𝑒 = 𝑢1𝑠 (1)𝑢𝑛𝑙 (2) = 1𝑠𝑛𝑙
𝜓𝑠𝑝𝑎𝑐𝑒 = 𝑢1𝑠 (2)𝑢𝑛𝑙 (1) = 𝑛𝑙1𝑠
They have the same energy: exchange degeneracy

So the total spatial wavefuction 𝜓?

We just take a linear combination
𝑠
1
𝜓𝑠𝑝𝑎𝑐𝑒 = 1𝑠𝑛𝑙 + 𝑛𝑙1𝑠
2
𝑎.𝑠
1
𝜓𝑠𝑝𝑎𝑐𝑒 = 1𝑠𝑛𝑙 − 𝑛𝑙1𝑠
2

18
 Helium: the excited state
Without e-e interaction,

𝐻0 = 𝐻1 + 𝐻2

𝐻0 |𝜓ۧ = 𝐸 (0) |𝜓ۧ with

𝐸 (0) = 𝐸1 + 𝐸2 (calculate following Rydberg formula)

19
 Helium: the excited state

𝑒 2
𝐻′ = total Hamiltonian: 𝐻 = 𝐻0 + 𝐻′
4𝜋𝜀0 𝑟12

Evaluate: perturbation theory

Δ𝐸 = ‫𝐻|𝜓ۦ‬′|𝜓ۧ

Spatial wavefunction can be symmetric or antisymmetric

𝑠
1
𝜓𝑠𝑝𝑎𝑐𝑒 = 1𝑠𝑛𝑙 + 𝑛𝑙1𝑠
2
𝑎.𝑠
1
𝜓𝑠𝑝𝑎𝑐𝑒 = 1𝑠𝑛𝑙 − 𝑛𝑙1𝑠
2

20
 Helium: the excited state
Δ𝐸 = ‫𝐻 𝜓ۦ‬′ 𝜓ۧ
1
= ‫ۦ‬1𝑠𝑛𝑙 ±‫𝑙𝑛ۦ‬1𝑠|)𝐻′ ( 1𝑠𝑛𝑙 ۧ ± 𝑛𝑙1𝑠ۧ
2
1
= ‫ۦ‬1𝑠𝑛𝑙|𝐻′ |1𝑠𝑛𝑙 ۧ + ‫𝑙𝑛ۦ‬1𝑠|𝐻′ |𝑛𝑙1𝑠ۧ
2
1
± ‫ۦ‬1𝑠𝑛𝑙|𝐻′ |𝑛𝑙1𝑠ۧ + ‫𝑙𝑛ۦ‬1𝑠|𝐻′ |1𝑠𝑛𝑠ۧ
2
= ‫ۦ‬1𝑠𝑛𝑙|𝐻′ |1𝑠𝑛𝑙 ۧ ± ‫ۦ‬1𝑠𝑛𝑙|𝐻′ |𝑛𝑙1𝑠ۧ
=𝐽±K

Exchange integral 𝐾
Direct integral 𝐽

𝛥𝐸 𝑆 = 𝐽 + 𝐾
𝛥𝐸 𝐴𝑆 = 𝐽 − 𝐾
21
 Helium: the excited state
What does J and K mean?

𝐽 ± 𝐾 = 1𝑠2𝑠 𝐻 ′ 1𝑠2𝑠 ± 1𝑠2𝑠 𝐻 ′ 2𝑠1𝑠

Charge density distribution:

𝜌1𝑠 (1) = −𝑒|𝜓1𝑠 (1)|2
𝜌2𝑠 (2) = −𝑒|𝜓2𝑠 (2)|2
Just the Coulomb repulsion of
the charge clouds

1 𝜌1𝑠 (1)𝜌2𝑠 (2) 3 3

𝐽= ඵ ⅆ𝑟1 ⅆ𝑟2
4𝜋𝜀0 𝑟12

𝐾
has no classical analog, it is due to the interference of the amplitudes

22
 Helium: the excited state
The result:

𝛥𝐸 𝑆 = 𝐽 + 𝐾 Singlet, with symmetric spatial WF

𝛥𝐸 𝐴𝑆 = 𝐽 − 𝐾

Triplet, with anti-symmetric spatial WF

Question:
1. Why J is positive?
2. Why singlet has higher energy?

What about for large n, l?

overlap between |1s> and |nl> is small

23
 He atom: summary
The Hamiltonian e--e- repulsion

ℏ2 2 ℏ2 2 𝑍𝑒 2 𝑍𝑒 2 𝑒2
𝐻 =− 𝛻 − 𝛻 − − +
2𝑚 1 2𝑚 2 4𝜋𝜖0 𝑟1 4𝜋𝜖0 𝑟2 4𝜋𝜖0 𝑟12

1. Bohr’s model fails; exact solution hard; need approximation methods

2. With simple perturbation theory and hydrogenic WF, we can already get
a quite good idea of the energy levels for both the ground and excited states

3. Two electron spins: spin singlet (S = 0) and triplet (S = 1)

4. Two electrons: direct (Coulomb) integral J and exchange integral K

24
He atom: summary

25
Alkali atoms: a short introduction

26
 Introduction
Building up principle of electron orbits: inert gas + one e-

Somewhat H-like:

The large n spectrum is almost like hydrogen: one charge

Ry
𝐸𝑛𝑙 = −
𝑛2
In reality, need to consider the quantum defect: 𝛿𝑛𝑙
Ry
𝐸𝑛𝑙 =−
(𝑛 − 𝛿𝑛𝑙 )2 27
 Quantum defect for alkalis
Quantum defect is a “phenomenological” theory
The quantum defects for alkalis have l dependence, i.e., the same n can have
different energy, not the same as H atom

Notation:
2𝑆+1
𝐿𝐽

For alkali atoms:

𝑆 = 𝑠 = 1/2 → 2𝑆 + 1 = 2
𝐿 = 𝑙 of the valence electron
J fine structure (later)

28
 Quantum defect for alkalis
With the quantum defect, we can express the energy levels using a
modified Rydberg formula
𝑅𝑦 𝑅𝑦
𝐸(𝑛, 𝑙) = − =− 2
(𝑛 − 𝛿𝑙 )2 𝑛∗

For Na
𝛿𝑠 = 1.35
𝛿𝑝 = 0.86
𝛿𝑑 = 0.01
𝛿𝑙 ≃ 0 for 𝑙 > 2

An important feature, the energy

levels become more and more like
hydrogen for larger l, why?

29
 Quantum defect for alkalis
With the quantum defect, we can express the energy levels using a
modified Rydberg formula
For Na
𝑅𝑦 𝛿𝑠 = 1.35
𝐸(𝑛, 𝑙) = − 𝛿𝑝 = 0.86
(𝑛 − 𝛿𝑙 )2
𝛿𝑑 = 0.01
𝛿𝑙 ≃ 0 for 𝑙 > 2

The probability density of the electrons vs r

Quantum defect represents the penetration of the valence electron into the core!
Larger l means small possibility of penetration!

From Foot: atomic physics 30

 Quantum defect for alkalis
Quantum defects for different alkalis:
𝑅𝑦
𝐸(𝑛, 𝑙) = −
(𝑛 − 𝛿𝑙 )2

Although quite different n, similar n*

𝑛∗ = 13.6 eV/IE 1/2

Therefore similar ionization energy

31
 Other methods: central field approximation
The Hamiltonian K.E. e--nucleus e--e- too large to be treated
as perturbation
ℏ2 𝑍𝑒 2 𝑒2
𝐻 = σ𝑁
𝑖=1 − 𝛻𝑖 2 − + 𝑁
σ𝑗>𝑖
2𝑚 4𝜋𝜖0 𝑟𝑖 4𝜋𝜖 𝑟0 𝑖𝑗

The idea: treat each electron as independent, but in an effective potential VCF
of the nucleus and the other electrons
𝑍𝑒 2
𝑉𝐶𝐹 =− + 𝑆(𝑟)
4𝜋𝜖0 𝑟
S(r): a central potential from the other electrons, which has spherical symmetry.
This follows because the closed sub-shells within the core have a spherical
charge distribution, and therefore the interactions between the different shells
and between shells and the valence electron are also spherically symmetric.
The Hamiltonian becomes
ℏ2
𝐻𝐶𝐹 = σ𝑁
𝑖=1 − 𝛻𝑖 2 + 𝑉𝐶𝐹 (𝑟𝑖 )
2𝑚

ℏ2 2
− 𝛻 + 𝑉𝐶𝐹 (𝑟1 ) = 𝐸1 𝜓1
2𝑚 1 32
 Central field approximation
The Hamiltonian becomes 𝐻 = σ𝑁 − ℏ2
𝐶𝐹 𝑖=1 𝛻𝑖 2 + 𝑉𝐶𝐹 (𝑟𝑖 )
2𝑚

The total WF 𝜓𝑎𝑡𝑜𝑚 = 𝜓1 𝜓2 𝜓3 ⋯ 𝜓𝑁

The total energy 𝐸𝑎𝑡𝑜𝑚 = 𝐸1 +𝐸2 +𝐸3 + ⋯ + 𝐸𝑁

Leads to N equations of the form:

ℏ2 2
− 𝛻 + 𝑉𝐶𝐹 (𝑟1 ) = 𝐸1 𝜓1
2𝑚 1

The WF for each electron 𝜓1 =𝑅(𝑟1 )𝑌𝑙𝑚

1
1𝜓
𝑠𝑝𝑖𝑛 (1)

For the radial part, take: 𝑃(𝑟) ≡ 𝑟𝑅(𝑟)

ℏ2 ⅆ 2 𝑙 𝑙 + 1 ℏ2
− + + 𝑉𝐶𝐹 (𝑟) 𝑃 𝑟 = 𝐸𝑃 𝑟
2𝑚 ⅆ𝑟 2 2𝑚𝑟 2

33
 Central field approximation: VCF
The effective potential:
𝑙 𝑙 + 1 ℏ2
+ 𝑉𝐶𝐹 (𝑟)
2𝑚𝑟 2
Need to know the form of VCF(r)
𝑍𝑒
Small r 𝑬 𝑟 →− 𝒓ො From full neclear charges
4𝜋𝜖0 𝑟 2
𝑒
Large r 𝑬 𝑟 →− 𝒓ො The other N-1 electrons screen
4𝜋𝜖0 𝑟 2 most of the nuclear charges:
1 positive charge
In total, effectively:
𝑍𝑒𝑓𝑓 𝑒 For Na
𝑬𝐶𝐹 𝑟 →− 2
𝒓ො
4𝜋𝜖0 𝑟
𝑟
𝑉𝐶𝐹 𝑟 = 𝑒 න 𝑬𝐶𝐹 𝑟′ ⅆ𝑟′
∞

34
 Central field approximation: VCF
𝑟
𝑉𝐶𝐹 𝑟 = 𝑒 න 𝑬𝐶𝐹 𝑟′ ⅆ𝑟′ 𝑙 𝑙 + 1 ℏ2
∞ + 𝑉𝐶𝐹 (𝑟)
2𝑚𝑟 2

For Na

35
 Central field approximation: VCF
For rigorous self-consistent Hartree-Fock method:

1. Guess VCF
2. Solve the S.E. numerically for slater determinant W.F.

3. Use the solution to refine VCF, solve & repeat until self-consistent.

4. Not only for atoms, (diatomic) molecules also

This is one kind of the Ab initio quantum chemistry methods

36
 Fine structure of H atoms
(and similarly in other atoms)

37
 What have we ignored so far?

1. Relativistic effects: electron is moving fast

2. Electron spin: fine structure
3. Nuclear spin: hyperfine structure
4. Quantum electrodynamics corrections: Lamb shift
5. Atoms in external B and E fields

38
 Fine structure: relativistic effect

The energy of a relativistic particle:

The relativistic correction:

𝑝4
𝐻rel =−
8𝑚3 𝑐 2

From the classic orbit picture:

𝑣 𝑒2 1
𝛼= = ≈
𝑐 4𝜋𝜖0 ℏ𝑐 137

𝛼 4 𝑚𝑐 2
𝐻rel =− 𝑛=1
8
1 𝑚 𝑒 2 Τ 4𝜋𝜖0 2
1 𝛼 2
𝐸𝑛 = − 2 = − 𝑚𝑐 2 2
2𝑛 ℏ2 2 𝑛
39
 Fine structure: spin-orbit coupling
So far ignored the electron spin in H:
➢ Spin itself does not affect the energy
Interaction between spin and the magnetic field of
the electron orbiting around the nuclear

𝑒ℏ
𝐻𝐵 = −𝛍 · 𝐁 = 𝝈·𝐁
2𝑚𝑒

Pauli Hamiltonian:

vector potential SOC scalar potential

Not relativistic
40
 The complete relativistic correction: Dirac equation

➢ Not going to solve it

➢ Focus more on the origin of the Fine Structure
➢ Use perturbation theory to calculate the corrections
H0

2 2
𝑝 𝑍𝑒
𝐻 = 𝑚𝑐 2 + −
2𝑚 4𝜋𝜀0 𝑟
𝑝4 ℎ2 𝑍𝑒 2 1 ℏ2 𝑍𝑒 2
− 3 2
+ 2 2 3
𝒍∙𝒔− 2 2
𝛻2
8𝑚 𝑐 2𝑚 𝑐 4𝜋𝜀0 𝑟 8𝑚 𝑐 4𝜋𝜀0 𝑟

K.E. Spin-orbit Darwin term

correction coupling HD
Hrel HSO

B.H.Bransden and C.J.Joachain, Physics of Atoms and Molecules 41